CN109273717A - A kind of lithium ion battery silicon substrate cathode modified binder and the preparation method containing the binder battery - Google Patents
A kind of lithium ion battery silicon substrate cathode modified binder and the preparation method containing the binder battery Download PDFInfo
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- CN109273717A CN109273717A CN201811002893.8A CN201811002893A CN109273717A CN 109273717 A CN109273717 A CN 109273717A CN 201811002893 A CN201811002893 A CN 201811002893A CN 109273717 A CN109273717 A CN 109273717A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
- H01M4/623—Binders being polymers fluorinated polymers
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
A kind of preparation method the present invention relates to lithium ion battery silicon substrate cathode modified binder and containing the binder battery.Cathode modified binder composition are as follows: binder 15%~35%, GQDs 5%~20%, deionized water 50%~70%.Mixed solution pH value is 4.5~8.5, and viscosity is 5mPa.S~55mPa.S.Modified binder of the present invention enhances material with material/foil adhesion strength by chemical bond, and higher cementability advantageously reduces contact resistance, and the capacity for improving electrode plays and high rate performance；Binder has preferably elasticity, swelling behavior after drying, is able to suppress electrode expansion, improves long-term cycle performance.In addition, binder of the present invention can reduce binder rising phenomenon in coating drying course, and then phenomena such as avoid nipping process roll banding or shedding, drop off.The method of the present invention simple process, additive amount is few, meets the market requirement, and is suitble to large-scale production.
Description
Technical field
Preparation side the present invention relates to a kind of modified negative electrode binder of lithium ion battery silicon substrate and containing the binder battery
Method belongs to technical field of lithium ion.
Background technique
Lithium ion battery has many advantages, such as that energy density is high, open-circuit voltage is high, has extended cycle life, and is widely used in calculating
In machine, mobile phone, EV and other portable electronic devices.
The raw material ratio of one complete lithium ion battery, it is necessary to including active material, conductive agent, binder, molten
The composition such as agent and additive.Wherein, binder is played in the battery by active material and foil, active material and active matter
The effect bonded between matter, between active material and conductive agent plays important core angle although dosage is seldom
Color has crucial effect to battery performance.
Currently, declining about lithium ion battery, to drop the research of mechanism mostly concentrated on positive and negative pole material, such as much researchs
Showing that active material loss, internal resistance such as increase at the factors is to cause lithium ion battery to decline the principal element of drop, and exist for binder
The lithium ion battery Effect study played in drop process that declines is also fewer.In fact, during charge and discharge due to lithium from
The insertion and abjection of son will lead to positive and negative anodes and apparent volume change occur, and the bulk strain of generation can destroy electrode material and stablize
Structure.Requirement and expectation especially now with application end to lithium ion battery improve day by day, it has in negative electrode active
Silica-base material is added in material to promote energy density.It is well known that the volume change of Si reaches in charge and discharge process
300% or more, internal stress caused by violent volume change, be easy to cause bonding agent/conductive agent and active material particle it
Between lamination occurs, so as to cause the loss of active material, expansion increases, and internal resistance increases, and causes the reversible of lithium ion battery
Capacity decline, cycle performance decaying.
The application of silicon carbon material, to negative electrode binder, more stringent requirements are proposed.According to the property of decentralized medium, binder
It can be divided into using organic solvent as the oiliness binder of dispersing agent and using water as the aqueous binders of dispersing agent.Traditional oiliness bonding
Agent is rigidly not suitable as more by force the binder of silicon carbon material system, some aqueous binders such as SBR, PAA etc., because dry
There is preferable elasticity afterwards, meanwhile, it is aqueous binders environmental protection, cheap and using safer therefore existing compared to oiliness binder
It has been widely used as negative electrode binder.But it is found after being used for a long time, prepares negative electricity pole piece and be easy to appear cathode slurry in the process
Material floats blue, cathode the problems such as rolling roll banding, and these problems main cause is that binder is unstable in negative electrode slurry, is be easy to cause
Agglomerant concentration distribution is poor after coating drying, and caking property is deteriorated between material and material/foil, so as to cause battery performance decline.Needle
To these problems, elastomer/emulsion technology ability is given full play to, is the pass realizing lithium ion battery and being applied to binder demand
Key.From industry situation, the application demand that generally has the following basic aqueous binders ability orientation: 1) to active matter
Matter and metal have a fabulous bonding force, 2) potential resistance to electrolyte contamination chemical stability, 3) in slurry colloid stability, 4) good processing
Performance.The present invention provides a kind of water-base cathode binder that surface is modified as improvement direction.
Summary of the invention
The purpose of the present invention is in view of the defects existing in the prior art: 1) binder is not sufficiently stable and causes to apply in negative electrode slurry
There is roll banding in cloth process occur floaing blue phenomenon, roller compaction process；2) binder elasticity is not enough to support silica-base material circulation expansion；3)
Binder conductivity is low to cause battery high rate capability undesirable etc., provides that a kind of adhesive property, expansion character is good and has
The binder of excellent processability.It is all obviously improved using the battery multiplying power and cycle performance of binder design.
In order to achieve the above objectives, the modification that is mixed with GQDs and binder under heating stirring of the ingenious property of the present invention is glued
Agent is tied, GQDs is allowed to have more affinity with active material and foil, therefore slurry is steady by changing adhesive particle surface texture
Qualitative, material is ensured very well with material/foil cohesive force；In addition to this, because chemical bond to have after binder is dry
There are better elasticity, swelling behavior, and then the volume expansion of negative electrode material (especially silicon carbon material) is inhibited very well, hence it is evident that change
Kind cycle performance of battery.
By widely studying with test discovery repeatedly, the modified binder prepared through the invention has certain electricity
Electron conductivity and ionic diffusion coefficient, are applied in lithium ion battery, greatly improve the high rate capability of battery.
Present invention provide the technical scheme that
A kind of lithium ion battery silicon substrate cathode modified binder, the cathode modified binder include by weight percentage
Following component: binder 15%~35%, graphene quantum dot GQDs 5%~20%, deionized water 50%~70%；By with
On at the mixed solution being grouped as pH value be 4.5~8.5, mixed solution viscosity be 5mPa.S~55mPa.S；Its preparation step
Are as follows: it first disperses graphene quantum dot GQDs in deionized water, 1~4h is stirred at room temperature, make it completely dissolved uniformly, be denoted as molten
Liquid A；Deionized water is added in dispersion pot, 60~90 DEG C is heated to, binder is added under stiring, after it is uniformly dispersed,
Solution A is added, continues to stir 4h, then be cooled to room temperature, obtains the cathode modified binder.
The molecular weight of the cathode modified binder is 100000~300000, and molecular particle size is less than 250nm.
The graphene quantum dot GQDs partial size is less than 20nm, and edge connects or be not connected to functionalization group.
The binder is styrene butadiene rubber sbr, polyacrylic acid PAA, polytetrafluoroethylene PTFE, polyimides PI, poly- second
One of enol PVA, polyacrylonitrile (PAN) or any several mixing.
The present invention also announces the lithium ion battery prepared using the lithium ion battery silicon substrate cathode modified binder, system
It is standby that steps are as follows:
1) prepared by anode pole piece: positive active material, conductive agent and binder dry powder blend are added in homogenate tank
It does even, decentralized medium is then added, continues to stir, obtains thick anode sizing agent；Or binder is individually distributed to dispersion
In medium, stirring is remixed with positive active material, conductive agent after mixing, obtains thick anode sizing agent；It will be thick
Slurry is uniformly coated in aluminum foil current collector, is dried, is rolled, cutting, welding electrode ear, preparing positive plate；
2) prepared by cathode pole piece: negative electrode active material, conductive agent, thickener dry powder blend being added in homogenate tank and done
It is even, decentralized medium is then added, continues to stir, is eventually adding the cathode modified binder, obtains after mixing evenly sticky
Shape negative electrode slurry；Or be individually distributed to thickener in decentralized medium, after mixing again with negative electrode active material, conductive agent
It is mixed, is eventually adding the cathode modified binder, obtains thick negative electrode slurry after mixing evenly；By thick slurry
Material is uniformly coated in copper foil current collector, is dried, is rolled, cutting, welding electrode ear, and negative electrode tab is prepared；
3) lithium ion battery assembles: anode pole piece, cathode pole piece and the alternate placement of diaphragm prepared by step 1), step 2)
Poling group is wound, is encased in battery case, encapsulation, fluid injection, high temperature ageing, pressurization chemical conversion, partial volume prepare lithium ion battery.
Positive active material described in step 1) is the mixing of one or more of cobalt acid lithium, nickel cobalt manganese, nickel cobalt aluminium,
The decentralized medium is N-Methyl pyrrolidone or deionized water.
Cathode modified binder described in step 2) accounts for 0.5~3wt% of total dry powder slurry.
Negative electrode active material described in step 2) is Si-C composite material, natural graphite, artificial graphite, surface modification
One of natural graphite, soft carbon, hard carbon or carbonaceous mesophase spherules or wherein several any combination；The conductive agent is
At least one of Ketjen black, acetylene black, superconducting carbon black, carbon nanotube, carbon fiber, graphene.
Thickener described in step 2) is sodium carboxymethylcellulose or carboxymethyl cellulose lithium or alginate；Described
Decentralized medium is deionized water or N-Methyl pyrrolidone.
There is thick negative electrode slurry described in step 2) room temperature to stand the stability that 10h is not settled.
Compared with prior art, cathode modified binder of the invention has following significant advantage:
(1) adhesion strength expands advantage.By the modification to binder particle surface functional group, modified binder can
It effectively is gathered in active contacts position, has more affinity with material, and have fabulous bonding force with metal, hence it is evident that enhancing is viscous
Tie performance.Higher cementability advantageously reduces contact resistance, and the capacity for improving electrode plays and high rate performance.Chemical bond simultaneously
Effect makes have preferably elasticity, swelling behavior after binder is dry, reaches and inhibits electrode expansion purpose.
(2) inhibition of metastasis advantage.Because GQDs is enriched in adhesive surface, binder can participate in thickener shape together
At gel structure, gel structure is able to maintain the uniform and stable property of slurry within a certain period of time, and in addition this gel structure also can
Binder rising phenomenon in coating drying course is reduced, avoids the occurrence of the generation of Cu interface adhesive deficient phenomena, and then avoid
Nipping process causes roll banding or shedding, phenomena such as drop off.The binder meets the market requirement to inhibiting migration to contribute.
(3) high rate performance advantage.Usual binder particle after pole piece is dry, in the battery can absorbed electrolyte swelling,
Excessive swelling will affect electron transmission, and internal resistance is caused to rise.The surface-crosslinked a certain amount of GQDs of modified binder, can be improved
The electric conductivity and ion transport capability of lithium ion battery, while there is certain affinity with electrolyte, internal resistance is raised to one
Fixed interception, therefore be conducive to battery high rate performance.
(4) additive amount advantage.The usage amount that binder can be reduced using cathode modified binder of the invention, is conducive to
The energy density of lithium ion battery entirety, and the method for the present invention simple process are improved, large-scale production is suitble to.
Detailed description of the invention
Fig. 1 is modified binder structural schematic diagram prepared by the present invention.
Fig. 2 is the elasticity modulus comparison diagram that film is prepared using binder in Examples 1 to 6 and comparative example.
Fig. 3 is the peel strength comparison diagram that Examples 1 to 6 and comparative example prepare negative electrode tab.
Fig. 4 is that Examples 1 to 6 and comparative example prepare battery fully charged required time comparison diagram at 1.2C.
Fig. 5 is (room temperature) the cyclic curve figure comparison of embodiment 1 and comparative example at 1.2C.
Specific embodiment
The present invention is further explained in the light of specific embodiments.
In the following examples, the experimental methods for specific conditions are not specified, usually according to normal condition, or according to manufacturer
Proposed condition.Heretofore described " room temperature ", " normal pressure " refer to temperature and air pressure between regular job, generally 25
DEG C, an atmospheric pressure.
Battery involved in following embodiment and comparative example is 405677 soft bag lithium ionic cells.
Embodiment 1
1) it disperses 2kgGQDs in 5kg deionized water, 2h is stirred at room temperature, make it completely dissolved uniformly, be labeled as solution
A；7kg deionized water is added in dispersion pot, 80 DEG C is heated to, is added with stirring 6kg binder SBR, it, will after being uniformly dispersed
Solution A is added, and continues to stir 4h, is cooled to room temperature, obtains modified binder.Wherein SBR molecular weight is 180000, partial size 0.08
μm, GQDs partial size 8nm, solution ph 6.0, viscosity 45mPa.S；
2) prepared by anode pole piece: in proportion by positive active material cobalt acid lithium, conductive agent carbon black and binder PVDF
97.5:1.2:1.3, which is mixed to join in homogenate tank, to be done even, and decentralized medium NMP is then added, makes solid content 70%~80%,
Continue to stir, obtains thick anode sizing agent；Thick slurry is uniformly coated in aluminum foil current collector, dries, roll, dividing
It cuts, welding electrode ear, prepares positive plate.
3) prepared by cathode pole piece: thickener CMC being individually distributed in decentralized medium deionized water and is stirred evenly, by silicon-carbon
Negative electrode active material, conductive agent, which are mixed to join in homogenate tank, to be done even, is then added decentralized medium water, modulation solid content to 45%
~55%, continue to stir, be eventually adding modified binder SBR, obtain thick negative electrode slurry after mixing evenly, wherein silicon-carbon is negative
Pole active material: conductive agent: thickener CMC: binder SBR=92:4:2:2；Finally thick slurry is uniformly coated on
It in copper foil current collector, dries, roll, cutting, welding electrode ear, preparing negative electrode tab.
4) lithium ion battery assembles: anode pole piece, cathode pole piece prepared by step 2), step 3) are pressed one together with diaphragm
Determine mode and wind poling group, be encased in battery case (plastic-aluminum packaging film is formed), encapsulation, fluid injection, high temperature ageing, pressurization chemical conversion,
Partial volume prepares lithium ion battery.
Embodiment 2
1) it disperses 4kgGQDs in 7kg deionized water, 2h is stirred at room temperature, make it completely dissolved uniformly, be labeled as solution
A；5kg deionized water is added in dispersion pot, 80 DEG C is heated to, is added with stirring 4kg binder PAA, it, will after being uniformly dispersed
Solution A is added, and continues to stir 4h, is cooled to room temperature, obtains modified binder.Wherein PAA molecular weight is 150000, partial size 0.12
μm, GQDs partial size 15nm, solution ph 5.0, viscosity 30mPa.S；
2) prepared by anode pole piece: in proportion by positive active material cobalt acid lithium, conductive agent carbon black and binder PVDF
97.5:1.2:1.3, which is mixed to join in homogenate tank, to be done even, and decentralized medium NMP is then added, makes solid content 70%~80%,
Continue to stir, obtains thick anode sizing agent；Thick slurry is uniformly coated in aluminum foil current collector, dries, roll, dividing
It cuts, welding electrode ear, prepares positive plate.
3) prepared by cathode pole piece: thickener CMC being individually distributed in decentralized medium deionized water and is stirred evenly, by silicon-carbon
Negative electrode active material, conductive agent, which are mixed to join in homogenate tank, to be done even, is then added decentralized medium water, modulation solid content to 45%
~55%, continue to stir, be eventually adding modified binder PAA, obtain thick negative electrode slurry after mixing evenly, wherein silicon-carbon is negative
Pole active material: conductive agent: thickener CMC: binder PAA=92:4:2:2；Finally thick slurry is uniformly coated on
It in copper foil current collector, dries, roll, cutting, welding electrode ear, preparing negative electrode tab.
4) lithium ion battery assembles: anode pole piece, cathode pole piece prepared by step 2), step 3) are pressed one together with diaphragm
Determine mode and wind poling group, be encased in battery case (plastic-aluminum packaging film is formed), encapsulation, fluid injection, high temperature ageing, pressurization chemical conversion,
Partial volume prepares lithium ion battery.
Embodiment 3
1) it disperses 4kgGQDs in 7kg deionized water, 2h is stirred at room temperature, make it completely dissolved uniformly, be labeled as solution
A；6kg deionized water is added in dispersion pot, 80 DEG C is heated to, is added with stirring 3kg binder SBR, it, will after being uniformly dispersed
Solution A is added, and continues to stir 4h, is cooled to room temperature, obtains modified binder.Wherein SBR molecular weight is 120000, partial size 0.15
μm, GQDs partial size 5nm, solution ph 5.0, viscosity 25mPa.S；
2) prepared by anode pole piece: in proportion by positive active material cobalt acid lithium, conductive agent carbon black and binder PVDF
97.5:1.2:1.3, which is mixed to join in homogenate tank, to be done even, and decentralized medium NMP is then added, makes solid content 70%~80%,
Continue to stir, obtains thick anode sizing agent；Thick slurry is uniformly coated in aluminum foil current collector, dries, roll, dividing
It cuts, welding electrode ear, prepares positive plate.
3) prepared by cathode pole piece: thickener CMC being individually distributed in decentralized medium deionized water and is stirred evenly, by silicon-carbon
Negative electrode active material, conductive agent, which are mixed to join in homogenate tank, to be done even, is then added decentralized medium water, modulation solid content to 45%
~55%, continue to stir, be eventually adding modified binder SBR, obtain thick negative electrode slurry after mixing evenly, wherein silicon-carbon is negative
Pole active material: conductive agent: thickener CMC: binder SBR=92:4:2:2；Finally thick slurry is uniformly coated on
It in copper foil current collector, dries, roll, cutting, welding electrode ear, preparing negative electrode tab.
4) lithium ion battery assembles: anode pole piece, cathode pole piece prepared by step 2), step 3) are pressed one together with diaphragm
Determine mode and wind poling group, be encased in battery case (plastic-aluminum packaging film is formed), encapsulation, fluid injection, high temperature ageing, pressurization chemical conversion,
Partial volume prepares lithium ion battery.
Embodiment 4
1) it disperses 2kgGQDs in 4kg deionized water, 2h is stirred at room temperature, make it completely dissolved uniformly, be labeled as solution
A；7kg deionized water is added in dispersion pot, 80 DEG C is heated to, is added with stirring 7kg binder SBR, it, will after being uniformly dispersed
Solution A is added, and continues to stir 4h, is cooled to room temperature, obtains modified binder.Wherein SBR molecular weight is 200000,0.1 μ of partial size
M, GQDs partial size 5nm, solution ph 6.0, viscosity 35mPa.S；
2) prepared by anode pole piece: in proportion by positive active material cobalt acid lithium, conductive agent carbon black and binder PVDF
97.5:1.2:1.3, which is mixed to join in homogenate tank, to be done even, and decentralized medium NMP is then added, makes solid content 70%~80%,
Continue to stir, obtains thick anode sizing agent；Thick slurry is uniformly coated in aluminum foil current collector, dries, roll, dividing
It cuts, welding electrode ear, prepares positive plate.
3) prepared by cathode pole piece: thickener CMC being individually distributed in decentralized medium deionized water and is stirred evenly, by silicon-carbon
Negative electrode active material, conductive agent, which are mixed to join in homogenate tank, to be done even, is then added decentralized medium water, modulation solid content to 45%
~55%, continue to stir, be eventually adding modified binder SBR, obtain thick negative electrode slurry after mixing evenly, wherein silicon-carbon is negative
Pole active material: conductive agent: thickener CMC: binder SBR=92:4:2:2；Finally thick slurry is uniformly coated on
It in copper foil current collector, dries, roll, cutting, welding electrode ear, preparing negative electrode tab.
4) lithium ion battery assembles: anode pole piece, cathode pole piece prepared by step 2), step 3) are pressed one together with diaphragm
Determine mode and wind poling group, be encased in battery case (plastic-aluminum packaging film is formed), encapsulation, fluid injection, high temperature ageing, pressurization chemical conversion,
Partial volume prepares lithium ion battery.
Embodiment 5
1) it disperses 1kgGQDs in 5kg deionized water, 2h is stirred at room temperature, make it completely dissolved uniformly, be labeled as solution
A；8kg deionized water is added in dispersion pot, 80 DEG C is heated to, is added with stirring 6kg binder PAA, it, will after being uniformly dispersed
Solution A is added, and continues to stir 4h, is cooled to room temperature, obtains modified binder.Wherein PAA molecular weight is 200000, partial size 0.12
μm, GQDs partial size 10nm, solution ph 6.5, viscosity 20mPa.S；
2) prepared by anode pole piece: in proportion by positive active material cobalt acid lithium, conductive agent carbon black and binder PVDF
97.5:1.2:1.3, which is mixed to join in homogenate tank, to be done even, and decentralized medium NMP is then added, makes solid content 70%~80%,
Continue to stir, obtains thick anode sizing agent；Thick slurry is uniformly coated in aluminum foil current collector, dries, roll, dividing
It cuts, welding electrode ear, prepares positive plate.
3) prepared by cathode pole piece: thickener CMC being individually distributed in decentralized medium deionized water and is stirred evenly, by silicon-carbon
Negative electrode active material, conductive agent, which are mixed to join in homogenate tank, to be done even, is then added decentralized medium water, modulation solid content to 45%
~55%, continue to stir, be eventually adding modified binder PAA, obtain thick negative electrode slurry after mixing evenly, wherein silicon-carbon is negative
Pole active material: conductive agent: thickener CMC: binder PAA=92:4:2:2；Finally thick slurry is uniformly coated on
It in copper foil current collector, dries, roll, cutting, welding electrode ear, preparing negative electrode tab.
4) lithium ion battery assembles: anode pole piece, cathode pole piece prepared by step 2), step 3) are pressed one together with diaphragm
Determine mode and wind poling group, be encased in battery case (plastic-aluminum packaging film is formed), encapsulation, fluid injection, high temperature ageing, pressurization chemical conversion,
Partial volume prepares lithium ion battery.
Embodiment 6
1) it disperses 3kgGQDs in 5kg deionized water, 2h is stirred at room temperature, make it completely dissolved uniformly, be labeled as solution
A；7kg deionized water is added in dispersion pot, 80 DEG C is heated to, is added with stirring 5kg binder SBR, it, will after being uniformly dispersed
Solution A is added, and continues to stir 4h, is cooled to room temperature, obtains modified binder.Wherein SBR molecular weight is 170000,0.1 μ of partial size
M, GQDs partial size 8nm, solution ph 5.5, viscosity 30mPa.S；
2) prepared by anode pole piece: in proportion by positive active material cobalt acid lithium, conductive agent carbon black and binder PVDF
97.5:1.2:1.3, which is mixed to join in homogenate tank, to be done even, and decentralized medium NMP is then added, makes solid content 70%~80%,
Continue to stir, obtains thick anode sizing agent；Thick slurry is uniformly coated in aluminum foil current collector, dries, roll, dividing
It cuts, welding electrode ear, prepares positive plate.
3) prepared by cathode pole piece: thickener CMC being individually distributed in decentralized medium deionized water and is stirred evenly, by silicon-carbon
Negative electrode active material, conductive agent, which are mixed to join in homogenate tank, to be done even, is then added decentralized medium water, modulation solid content to 45%
~55%, continue to stir, be eventually adding modified binder SBR, obtain thick negative electrode slurry after mixing evenly, wherein silicon-carbon is negative
Pole active material: conductive agent: thickener CMC: binder SBR=92:4:2:2；Finally thick slurry is uniformly coated on
It in copper foil current collector, dries, roll, cutting, welding electrode ear, preparing negative electrode tab.
4) lithium ion battery assembles: anode pole piece, cathode pole piece prepared by step 2), step 3) are pressed one together with diaphragm
Determine mode and wind poling group, be encased in battery case (plastic-aluminum packaging film is formed), encapsulation, fluid injection, high temperature ageing, pressurization chemical conversion,
Partial volume prepares lithium ion battery.
Comparative example
This comparative example as the battery design technique that embodiment 1 is taken, raw material, production stage, unique difference
Place is the binder not synthesized using the present invention in this comparative example, and conventional binders SBR is only used only.
By the data of Fig. 2~3 it is found that the binder that the present invention synthesizes has good adhesive strength.It can by the data of Fig. 4~5
Know, the multiplying power of battery is designed using the binder that the present invention synthesizes and cycle performance has clear improvement.
The above is only some preferred embodiments of the invention, is not intended to limit the present invention in any form, and is appointed
What those skilled in the art, without departing from the scope of the present invention, according to the technical essence of the invention, to
Any simple modifications, equivalent substitutions and improvements etc. made by upper embodiment, still fall within the protection model of technical solution of the present invention
Within enclosing.
Claims (10)
1. a kind of lithium ion battery silicon substrate cathode modified binder, it is characterised in that: the cathode modified binder by weight hundred
Divide than counting comprising following component: binder 15%~35%, graphene quantum dot GQDs 5%~20%, deionized water 50%~
70%；By above at the pH value for the mixed solution being grouped as be 4.5~8.5, mixed solution viscosity be 5mPa.S~55mPa.S；
Its preparation step are as follows: first disperse graphene quantum dot GQDs in deionized water, 1~4h is stirred at room temperature, make it completely dissolved
Uniformly, it is denoted as solution A；Deionized water is added in dispersion pot, 60~90 DEG C is heated to, binder is added under stiring, to it
After being uniformly dispersed, solution A is added, continues to stir 4h, then be cooled to room temperature, obtains the cathode modified binder.
2. lithium ion battery silicon substrate cathode modified binder according to claim 1, it is characterised in that: the cathode is modified
The molecular weight of binder is 100000~300000, and molecular particle size is less than 250nm.
3. lithium ion battery silicon substrate cathode modified binder according to claim 1, it is characterised in that: the graphene
Quantum dot GQDs partial size is less than 20nm, and edge connects or be not connected to functionalization group.
4. lithium ion battery silicon substrate cathode modified binder according to claim 1, it is characterised in that: the binder
For in styrene butadiene rubber sbr, polyacrylic acid PAA, polytetrafluoroethylene PTFE, polyimides PI, PVAC polyvinylalcohol, polyacrylonitrile (PAN)
One or any of several mixing.
5. using the lithium-ion electric of the described in any item lithium ion battery silicon substrate cathode modified binder preparations of claim 1-4
Pond, it is characterised in that: preparation step is as follows:
1) anode pole piece prepare: by positive active material, conductive agent and binder dry powder blend be added to homogenate tank in do it is even,
Then decentralized medium is added, continues to stir, obtains thick anode sizing agent；Or binder is individually distributed to decentralized medium
In, stirring is remixed with positive active material, conductive agent after mixing, obtains thick anode sizing agent；By thick slurry
It is uniformly coated in aluminum foil current collector, dries, rolls, cutting, welding electrode ear, preparing positive plate；
2) cathode pole piece prepare: by negative electrode active material, conductive agent, thickener dry powder blend be added to homogenate tank in do it is even, so
After decentralized medium is added, continue to stir, be eventually adding the cathode modified binder, obtain thick cathode after mixing evenly
Slurry；Or be individually distributed to thickener in decentralized medium, it remixes stir with negative electrode active material, conductive agent after mixing
It mixes, is eventually adding the cathode modified binder, obtains thick negative electrode slurry after mixing evenly；Thick slurry is uniform
Be coated in copper foil current collector, dry, roll, cutting, welding electrode ear, prepare negative electrode tab；
3) lithium ion battery assembles: the alternate placement of anode pole piece, cathode pole piece and diaphragm prepared by step 1), step 2) is wound
Poling group, is encased in battery case, and encapsulation, fluid injection, high temperature ageing, pressurization chemical conversion, partial volume prepare lithium ion battery.
6. lithium ion battery according to claim 5, it is characterised in that: positive active material described in step 1) is cobalt
The mixing of one or more of sour lithium, nickel cobalt manganese, nickel cobalt aluminium, the decentralized medium are N-Methyl pyrrolidone or deionization
Water.
7. lithium ion battery according to claim 5, it is characterised in that: cathode modified binder described in step 2) accounts for
0.5~3wt% of total dry powder slurry.
8. lithium ion battery according to claim 5, it is characterised in that: negative electrode active material described in step 2) is silicon
In the modified natural graphite in carbon composite, natural graphite, artificial graphite, surface, soft carbon, hard carbon or carbonaceous mesophase spherules
A kind of or wherein several any combination；The conductive agent is Ketjen black, acetylene black, superconducting carbon black, carbon nanotube, carbon fiber
At least one of dimension, graphene.
9. lithium ion battery according to claim 5, it is characterised in that: thickener described in step 2) is that carboxymethyl is fine
Tie up plain sodium or carboxymethyl cellulose lithium or alginate；The decentralized medium is deionized water or N-Methyl pyrrolidone.
10. lithium ion battery according to claim 5, it is characterised in that: thick negative electrode slurry described in step 2)
The stability that 10h is not settled is stood with room temperature.
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